CN1332948C - Double indolyl derivative synthesizing process - Google Patents
Double indolyl derivative synthesizing process Download PDFInfo
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- CN1332948C CN1332948C CNB2005100400537A CN200510040053A CN1332948C CN 1332948 C CN1332948 C CN 1332948C CN B2005100400537 A CNB2005100400537 A CN B2005100400537A CN 200510040053 A CN200510040053 A CN 200510040053A CN 1332948 C CN1332948 C CN 1332948C
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- Prior art keywords
- aldehyde
- double
- reaction
- catalyst
- indolyl
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- 125000001041 indolyl group Chemical group 0.000 title claims description 12
- 238000000034 method Methods 0.000 title abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 17
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 150000002475 indoles Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000003930 superacid Substances 0.000 abstract description 7
- 239000003377 acid catalyst Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract description 3
- -1 aliphatic aldehydes Chemical class 0.000 abstract description 2
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 6
- PHXLXBRHTYYWJW-UHFFFAOYSA-N 3-[1h-indol-3-yl(phenyl)methyl]-1h-indole Chemical compound C=1NC2=CC=CC=C2C=1C(C=1C2=CC=CC=C2NC=1)C1=CC=CC=C1 PHXLXBRHTYYWJW-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- TWJAXIHBWPVMIR-UHFFFAOYSA-N 2-(1h-indol-2-ylmethyl)-1h-indole Chemical compound C1=CC=C2NC(CC=3NC4=CC=CC=C4C=3)=CC2=C1 TWJAXIHBWPVMIR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940074386 skatole Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- DJNXODINAWYXRH-UHFFFAOYSA-N thiophene;toluene Chemical compound C=1C=CSC=1.CC1=CC=CC=C1 DJNXODINAWYXRH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Abstract
本发明公开了一种双吲哚烷基衍生物的合成方法，由醛与吲哚进行合成反应，所述的醛选自C1至C10的脂肪醛或芳香醛，其特征在于：采用固体超强酸SO4 2-/TiO2作为催化剂，对应每毫摩尔的醛，催化剂的加入量为30-80毫克，研磨反应0.5小时至5小时，然后用溶剂洗涤，过滤，滤液浓缩即得到双吲哚烷基衍生物。本发明采用易于实现循环利用的固体超强酸催化剂代替传统质子酸或Lewis酸催化剂在无溶剂条件下来制备双吲哚烷基衍生物，避免了有机溶剂对环境产生的污染；反应产率高，时间短，操作简单。The invention discloses a method for synthesizing bisindole alkyl derivatives. The synthesis reaction is carried out by aldehyde and indole. The aldehyde is selected from C1 to C10 aliphatic aldehydes or aromatic aldehydes, and is characterized in that: solid The superacid SO 4 2- /TiO 2 is used as a catalyst, and the amount of the catalyst added is 30-80 mg for every millimole of aldehyde, and the reaction is ground for 0.5 hours to 5 hours, then washed with a solvent, filtered, and the filtrate is concentrated to obtain bisindoline Inoleyl derivatives. The present invention adopts the solid superacid catalyst that is easy to realize recycling to replace the traditional protonic acid or Lewis acid catalyst to prepare bisindole alkyl derivatives under solvent-free conditions, avoiding the pollution of the environment by organic solvents; the reaction yield is high and the time is short. Short and easy to operate.
Description
Technical field
The present invention relates to a kind of pentatomic ring that contains, condense with other ring, heteroatoms is the preparation of the heterogeneous ring compound of nitrogen-atoms, is specifically related to a kind of synthetic method of bis-indolyl alkyl compounds.
Background technology
Benzazole compounds is widespread in nature, and the derivative of many indoles all has certain physiologically active.Bis-indolyl alkyl compounds and derivative thereof are present in the continent and the ocean protista has in the bioactive metabolite, these compounds have certain activity, as: therefore multiple physiologically actives such as antitumor, antiviral, antibiotic and anti-inflammatory have caused organic chemist and medicine scholar keen interest.Wherein bis (indolyl) methane has formed the commodity of suitability for industrialized production.
The synthetic of bis-indolyl alkyl compounds just has report as far back as 19th century, and over more than 100 year, bis-indolyl alkyl compounds synthetic obtained significant progress.Main synthetic method be by indoles and aldehydes or ketones protonic acid or Lewis acid as: polynite K-10, LiClO
4, In (OTf)
3, InCl
3, I
2, CAN, FeCl
3Deng catalysis under obtain with productive rate preferably.But these methods all exist certain deficiency, have all limited the popularization of these methods to a certain extent as the poisonous and hazardous volatile organic solvent of a large amount of uses, use that expensive catalysts, harsh reaction conditions, complicated operations program and catalyzer can not be recycled etc.This just needs people to go to seek a kind of reaction system that more meets the Green Chemistry developing direction, for later suitability for industrialized production is laid a solid foundation.
In recent years, along with the enhancing of people's environmental consciousness and environmental legislation are strict day by day, the pollution problem in the chemical industry is Cheng Wei Yi Han problem to be solved.People wish that each molecule in the raw material can both be converted into product, realize the zero release of pollution, adopt nontoxic raw material, the friendly product of production environment.And catalyzer is stated in the purpose in realization and is played a crucial role.Acid catalyst is as H
2SO
4, HF, H
3PO
4Be widely used Deng in catalytic field, but use this class catalyzer to exist some row such as producing a large amount of waste liquids, equipment corrosion seriously reaches catalyzer and the isolating difficulty of product, be difficult to realize shortcomings such as continuous production on the chemical technology, and solid acid catalyst can address the above problem to a great extent.Thereby replacing liquid acid catalyst with solid acid is a most important approach that realizes the environmental friendliness Catalytic processes.Along with the development of catalytic science and the enhancing day by day of environmental protection consciousness, the technology of employing solid acid catalyst becomes the focus of present research.This type of technology is in not homophase because of catalyzer and reactant, and is recyclable and reuse, and do not have equipment corrosion and problem of environmental pollution, thereby be called as cleaning procedure.This technology is at first succeeded in developing in refining of petroleum and petrochemical industry, after be introduced into the Minute Organic Synthesis field.Super acids is the acid also stronger than 100% sulfuric acid, in catalyzed reaction, and to olefines double bond isomerizing, hydrolysis, olefin alkylation, acidylate, aspects such as esterification all show higher activity, such catalyst reaction mild condition has wide practical use.Yet, but do not see the pertinent literature report with this synthetic reaction as the catalyst bis-indolyl alkyl compounds.
Summary of the invention
The present invention seeks to solid super acid catalyst was introduced in synthesizing of double indolyl derivative,, need not the double indolyl derivative synthetic method that organic solvent participates in so that a kind of productive rate height to be provided.
For achieving the above object, the technical solution used in the present invention is: a kind of synthetic method of double indolyl derivative, carry out building-up reactions by aldehyde and indoles, and described aldehyde is selected from C
1To C
10Alkanoic or aromatic aldehyde, adopt solid super-strong acid SO
4 2-/ TiO
2As catalyzer, the aldehyde of corresponding every mmole, the add-on of catalyzer is the 30-80 milligram, and griding reaction 0.5 hour to 5 hours is used solvent wash then, filters, and filtrate concentrating promptly obtains double indolyl derivative.
In the technique scheme, the temperature during described griding reaction is between 25 ℃ to 60 ℃.Temperature can influence the speed of reaction, and usually, when temperature was higher, speed of response was very fast, for example, 50 ℃ of following reaction times between 0.5 hour to 1.5 hours, but the too high meeting of temperature causes the decomposition of aldehyde, therefore, is advisable to be controlled at below 60 ℃.When carrying out suitability for industrialized production, grinding can adopt ball mill to carry out.
Carry out for reacting fully, to improve degree of purity of production, optimized technical scheme is that the mol ratio of described aldehyde and indoles is 1: 2.
In the technique scheme, described solvent is an ethyl acetate.
In the technique scheme, the solid of gained is exactly a solid super acid catalyst during filtration, and the catalyzer process is simple dry, and in the catalyzed reaction that activation promptly can be used for next time in two minutes in microwave oven.
The solid super-strong acid SO of this programme
4 2-/ TiO
2Preparation of catalysts has bibliographical information, can adopt following method: add TiCl in the round-bottomed flask that magnetic stirring apparatus, dropping funnel are housed
4Liquid slowly splashes into strong aqua then under violent stirring, equal 8 until the pH value of reaction mixture.The precipitate with deionized water washing of gained is to can not detecting Cl
-Existence till, then 100 ℃ dry 24 hours down.Gained blocks of solid grind into powder joins the H of an amount of 0.5mol/L then
2SO
4In, going out to anhydrate under the decompression, the gained sample promptly got solid super acid catalyst in 4 hours in 600 ℃ of following calcinations afterwards in 100 ℃ times dry 12 hours.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1. because adopting, the present invention is easy to realize that the solid super acid catalyst of recycle replaces traditional protonic acid or Lewis acid catalyst to prepare double indolyl derivative under condition of no solvent, the pollution of having avoided organic solvent that environment is produced;
2. productive rate height of the present invention, the time is short, and is simple to operate, and catalyzer can recycle several times easily, and activity can not reduce.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: bis (indolyl) methane synthetic
Get the formaldehyde of 1 mmole and the indoles of 2 mmoles and place Yan Portland, add solid super-strong acid SO
4 2-/ TiO
2Catalyzer, 50 milligrams of consumptions at 50 ℃ of following griding reaction 0.5-1.5 hours, with the ethyl acetate washing, filter then, and filtrate concentrating obtains thick product, further purifies to obtain the bis (indolyl) methane of higher degree.
Embodiment two: 3,3'-(Phenylmethylene)bis[1H-indole] synthetic
Get the phenyl aldehyde of 1 mmole and the indoles of 2 mmoles and place reaction flask, add the solid super-strong acid SO of 60mg
4 2-/ TiO
2, place Yan Portland, grind evenly, in being warming up under the infrared lamp about 50 ℃, through 0.5 hour, the TLC detection reaction was complete, with the ethyl acetate washing, filtered, and the filtrate vacuum concentration obtains thick product, and further purification promptly obtains the 3,3'-(Phenylmethylene)bis[1H-indole] of higher degree.
Embodiment three: two indoles thiophene phenyl methane synthetic
Get the thiophene phenol-2-formaldehyde of 1 mmole and the indoles of 2 mmoles and place reaction flask, add the solid super-strong acid SO of 45mg
4 2-/ TiO
2, place Yan Portland, grind evenly, in being warming up under the infrared lamp about 50 ℃, through 1.5 hours, the TLC detection reaction was complete, with the ethyl acetate washing, filtered, and the filtrate vacuum concentration obtains thick product, and further purification promptly obtains the 3,3'-(Phenylmethylene)bis[1H-indole] of higher degree.
Embodiment four: two indoles nonyl methane synthetic
Get the aldehyde C-9 of 1 mmole and the indoles of 2 mmoles and place reaction flask, add the solid super-strong acid SO of 50mg
4 2-/ TiO
2, place Yan Portland, grind evenly, in being warming up under the infrared lamp about 50 ℃, through 1.5 hours, the TLC detection reaction was complete, with the ethyl acetate washing, filtered, and the filtrate vacuum concentration obtains thick product, and further purification promptly obtains the 3,3'-(Phenylmethylene)bis[1H-indole] of higher degree.
Embodiment five: two 5-skatole p-nitrophenyl methylmethanes synthetic
Get the paranitrobenzaldehyde of 1 mmole and the 5-skatole of 2 mmoles and place reaction flask, add the solid super-strong acid SO of 50mg
4 2-/ TiO
2, place Yan Portland, grind evenly, in being warming up under the infrared lamp about 50 ℃, through 0.5 hour, the TLC detection reaction was complete, with the ethyl acetate washing, filtered, and the filtrate vacuum concentration obtains thick product, and further purification promptly obtains the 3,3'-(Phenylmethylene)bis[1H-indole] of higher degree.
Claims (4)
1. the synthetic method of a double indolyl derivative is carried out building-up reactions by aldehyde and indoles, and described aldehyde is selected from C
1To C
10Alkanoic or aromatic aldehyde, it is characterized in that: adopt solid super-strong acid SO
4 2-/ TiO
2As catalyzer, the aldehyde of corresponding every mmole, the add-on of catalyzer is the 30-80 milligram, and griding reaction 0.5 hour to 5 hours is used solvent wash then, filters, and filtrate concentrating promptly obtains double indolyl derivative.
2. the synthetic method of double indolyl derivative according to claim 1 is characterized in that: the temperature during described griding reaction is between 25 ℃ to 60 ℃.
3. the synthetic method of double indolyl derivative according to claim 1, it is characterized in that: the mol ratio of described aldehyde and indoles is 1: 2.
4. the synthetic method of double indolyl derivative according to claim 1, it is characterized in that: described solvent is an ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100400537A CN1332948C (en) | 2005-05-12 | 2005-05-12 | Double indolyl derivative synthesizing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100400537A CN1332948C (en) | 2005-05-12 | 2005-05-12 | Double indolyl derivative synthesizing process |
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| Publication Number | Publication Date |
|---|---|
| CN1706829A CN1706829A (en) | 2005-12-14 |
| CN1332948C true CN1332948C (en) | 2007-08-22 |
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ID=35580960
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100400537A Expired - Fee Related CN1332948C (en) | 2005-05-12 | 2005-05-12 | Double indolyl derivative synthesizing process |
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| Country | Link |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467354B (en) * | 2013-09-16 | 2015-04-08 | 陕西师范大学 | Method for preparing diindolyl methane derivatives |
| CN111606838B (en) * | 2020-06-19 | 2023-06-30 | 宁夏大学 | A kind of preparation method of bis-indolylmethane compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268134A (en) * | 1997-06-25 | 2000-09-27 | 罗赫诊断器材股份有限公司 | Bis-indole derivatives having antimetastatic activity, A process for their preparation and pharmaceutical compositions containing them |
| CN1469870A (en) * | 2000-10-18 | 2004-01-21 | �������⻯ѧƷ�ع�����˾ | The preparation method of bisindole compound |
-
2005
- 2005-05-12 CN CNB2005100400537A patent/CN1332948C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268134A (en) * | 1997-06-25 | 2000-09-27 | 罗赫诊断器材股份有限公司 | Bis-indole derivatives having antimetastatic activity, A process for their preparation and pharmaceutical compositions containing them |
| CN1469870A (en) * | 2000-10-18 | 2004-01-21 | �������⻯ѧƷ�ع�����˾ | The preparation method of bisindole compound |
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Application publication date: 20051214 Assignee: Suzhou Kaiyuan Minsheng Science and Technology Co., Ltd. Assignor: Soochow University Contract record no.: 2010320000323 Denomination of invention: Double indolyl derivative synthesizing process Granted publication date: 20070822 License type: Exclusive License Record date: 20100331 |
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Granted publication date: 20070822 Termination date: 20130512 |